Heterocyclic organotin compounds



' 3,201,408 HETEROCYCLIC ORGANOTIN COMPOUNDS Carl C. Greeo, Bronx, N.Y., assignor'torstaufier ,Chem-- ical Company, New- York, N.Y., a. corporation: of

Delaware No Drawing; Filed June 5, 1963,-Ser- N0."285,584-' 6 Claims. (Cl. 260-299)" compounds.

The novel organotini heterocyclic. derivatives as con templated herein can'be. represented by thefollowing.

and I wherein R signifies an: allr'yl radical ofzifr'omrl to l()"car.-" bon atoms, e.g; methyl; ethyl, nepropyl;@secabutyl; iso butyl, n-pentyl, isohexyl, n-heptyl, n-oetyl, isoocty'LQnnonyl, n-decyl and the .like,=and*a phenyl radiealfiwhieh can have attached thereto a;relatively, inert substituent:

such as lower ,alkyl, lower alkoxyl, chlorineor'the like and R represents lower alkyl or'phenyl;

Compounds whichtypify the above r'descrihedconfiguration" are included in. the. appended. examples and: in the following list of specific formulae:

S;I=N

In preparing, the organtinthiadiazoles of the invention, an oragnotin intermediate suchas: a. dialkyltin: oxide: on. dialkyltinr chloride 1 is reacted with a; thiadiazolem reactants. having attached to .the ringlher'eofia freezmercaptoxgroup Thea-reaction cambetschematical or itsalkali metal salt. ly depicted by the. following-:chemieal;equations:

Bil-

1 ice whereiniR-iand R havethesignificanceass-previously defined and M represents. an alkali metal or ammonium.

radio-ah Generally'speaking; excellent'yields: arerealized by re fluxingequivalent amounts of the reactantsinrthe presence of a normally liquid organic solvent. andlfor this purposev v the slowersaturated alciohols, including their ether; derivae tives, and liquid hydrocarbons of' thesaturated. aliphatic anduaromatic serieshave: proved to besatisfactory. As examples of specific solvents, mention Lism'ade of methanol,

n-propanol, ethanol, benzene; toluene; xylene, Cellosolve- It is 'to'be pointed: outthat. wherever the and the like; organotin intermediate is. the oxide, thenithethiadiazole is preferably used having :a: free mercapto function; on the other-hand; when: employing a; dialkyltin chloride,

it. isirec'ommended that thesthiadiazole have-the-:mercapto substituent in they form. of? its alkali metal :salt; By the I term" alkali metal salt is; also. includedzihe ammonium: andixsubstituted' ammonium: salts,e;g.: ammonium, lower alkylated: ammonium; e.=g. tetr-"amethylammonium;v tribenzylmethylammonium; pyridiniumeand'xthelike;

Referencelis now 'maderto the followinggexamples which:

are inserted for purposes of illustrationaonly and:thoseskilled-iinzthe 'art willtappreciate that various modifications of the invention can be:practiced without departing from the spirit andascopezrthereof.

Ina a. 500" cc. flask, equipped :with' stirrer; thermometer and:arsDe'an-Stark apparatus was. suspended 1714 g: (007 m:) of'dibutyltintoxide and '10 g;, (0;07 m 'of2,5-dimercapto=1,3,4-'thiadiazole= in" "cc; of toluene. The re-' action'mixture'FWas'sl'oWly heated to'reflux. vAfter 3 hours of-refluxing thettheoreticalamount of water was-azeotroped off. The reaction'mixturewas filteredihot, andrthe solvent was removed. by' vacuum distillation: The remaining" colorless, crystalline :solid. was vcollected as the product;

MP2 .1 20 C. Elemental analyses and :spectra confirmed the proposed'strueture: madam Analysis oftinz. calc'.:-3l.'4%; founde-30;6

This'product wasaprepared'analqgousftor Example 1. from .17 g; (0.042. m;-) of dioctyltin'" oxide. and 6.2 g'..

18g; (80% yields) was 'a"'colorless,". crystalline 'solid, MP. 52". C. Theastructurewas confirmed by' elemental and:

ILR: analyses:

EXAMPLES 1- nibm mnu,3 4hiadiawl iz;wmrca nae r 3,201,408 P'fllilliQdgAug; 17' 65 3 This product was prepared analogous to Example 1 from 7.5 g. (0.05 m.) of 2,5-dimercapto-1,3,4-thiadiazole and 14.5 g. (0.05 m.) of diphenyltin oxide. The product, 19g. (90% yield) was a viscous, yellow oil.

EXAMPLE 4 Dioctylnn bis(3-phenyl-1,3,4thiadiaz0Ie-Z-thione 5 -mercaptide) In a 250 cc. flask, equipped with stirrer, thermometer and reflux condenser was dissolved the potassium salt of 5-mercapto-3-phenyl-1,3,4-thiadiazole-Z-thione, 9 g. (0.034 m.), in 100 cc. of ethanol. Then 7 g. (0.017 m.) of dioctyltin dichloride, dissolved in cc. of ethanol, was added dropwise at C. After the addition was complete the reaction mixture was refluxed for 3 hours. The reaction mixture was then poured into water, extracted with benzene, dried over Na SO and solvent stripped. The remaining crude solid was crystallized from cc. of ethanol. The yield of colorless crystals, melting at C., amounted to 12 g. (90%). Elemental analyses and spectra confirmed the proposed structure.

EXAMPLE 5 This p,roduct was prepared analogous to Example 4 from 20.2 g. (0.1 m.) of the potassium salt of S-mercapto-S-methyl-l,3,4-thiadiazole-2-thione and 15.2 g. (0.05 m.) of dibutyltin dichloride. Product, 19.4 g. (85% yield), was a colorless, crystalline solid, M.P. C. Elemental analyses and spectra confirmed the proposed structure.

In addition to constituting a new and novel class of organotin derivatives, the compounds of the invention are useful in various applied arts and fields. I have, for instance, ascertained that the compounds are useful as stabilizers for plastics such as polyolefins. In this connection, reference is called to the compound of Example l which, when incorporated into isotactic polypropylene, increased the resistance of the polymer to degradation and embrittlement at moderately elevated temperatures, i.e. in the vicinity of C.

I claim: l. A heterocyclic organotin compound selected fro the group consisting of:

wherein R is selected from the class consisting of alkyl having from 1 to 10 carbon atoms and phenyl and R is selected from the class consisting of lower alkyl and l s l /a N 5. A heterocyclic organotin compound of the formula:

6. A heterocyclic organotin compound of the formula:

References Cited by the Examiner UNITED STATES PATENTS 2,713,580 7/55 Stefl et a.l. 260-299 NICHOLAS s. mzzo, Primary Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,201,408 August 17, 1965 Carl C. Greco It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, EXAMPLE 1, for that portion of the formula reading [nC H Sn read n- (C H Sn same column 2, EXAMPLE 3, for "Dibutyltin(l,3,4-thiadiazole- 2,5 di mercaptide) in italics, read Diphenyltin(l ,3,4- thladiazole-z ,S-dimercaptide) in italics.

Signed and sealed this 22nd day of February 1966. Attest:

ERNEST W. SWIDER Attesting Officer EDWARD J. BRENNER Commissioner of Patents 

1. A HETEROCYCLIC ORGANOTIN COMPOUND SELECTED FROM THE GROUP CONSISTING OF: 